CN106310364B - A kind of porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium - Google Patents

A kind of porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium Download PDF

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CN106310364B
CN106310364B CN201610525104.3A CN201610525104A CN106310364B CN 106310364 B CN106310364 B CN 106310364B CN 201610525104 A CN201610525104 A CN 201610525104A CN 106310364 B CN106310364 B CN 106310364B
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magnesium
strontium
source
calcium
sulphur
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CN106310364A (en
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李桑
蒋国强
汤亭亭
傅俊
彭兆祥
毛海蛟
熊汉锋
聂磊
李亚屏
郑建民
张国锋
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Abstract

The invention discloses a kind of porous compound bio brackets of degradable sulphur apatite containing magnesium and strontium, are obtained by the way that ox is calcined Grafting Cancellous Bone Bolt mine porous support through the quaternary system processing containing magnesium source, barium source, sulphur source and phosphorus source, after taking-up is dry, high-temperature calcination.It is mesh-structured with osteoconductive, degradability, preferable mechanical strength and biocompatibility that the porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium of the invention has both good three-dimensional intercommunication；There is the calcium sulfate crystal whiskers growth compared with big L/D ratio in mesh simultaneously, the specific surface area of material can be increased, cell adherence may be improved.Animal Bone defective region Bone Defect Repari works well and no inflammation reaction, immunological rejection.The compound bio bracket may more meet the ideal condition of bone transplantation substitute material or bone tissue engineering stent material.

Description

A kind of porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium
Technical field
The present invention relates to field of medical materials, in particular to a kind of porous compound life of the degradable sulphur apatite containing magnesium and strontium Object bracket.
Background technique
Bone collection is only less than the tissue transplantation of blood transfusion, and research, the exploitation of bone alternate material are the weights of current medical research One of, just about the research of bone alternate material and the body mechanism of action in the national brainstorm project of China 12.
Constituting people's bone bone mine has the elements such as Ca, P, O, H, C, S, Fe, Mg, Cu, Si, Zn, Mn, Na, K, in people's bone mineralising mistake There are extensive homogeneity replacement in journey, people's bone has complicated composition and structure.In bone tissue engineering scaffold or artificial bone Design process in, be critical to consider the complicated composition of this serious mineralized tissue of people's bone and structure；People's bone cannot be by single material Finite nature provided by expecting substitutes completely, it is even more important that it is more that bracket must also provide three-dimensional for the regeneration of bone tissue Hole micro-structure is wanted to maintain or comparatively fast obtain enough mechanical strengths and be substituted to meet to guide the differentiation and proliferation of cell The mechanical requirements of material.Ideal bone transplantation substitute material or bone tissue engineering stent material should have the following conditions: 1) having Good osteoconductive, material have aperture preferably three-dimensional intercommunication mesh-structured, as high as possible porosity and specific surface area 2) there is osteoinductive；3) surface chemistries with good biocompatibility and support bone cell growth and function differentiation Matter and micro-structure；4) there is good biological degradability；5) part that bone conduction effect is undertaken in material must have enough power Learn intensity and bearing capacity；6) easy processing etc..
The clinical available bone transplantation substitute material of New Zealand is summarized as four in a summary within Johan etc. 2010 Class: 1, single-phase calcium phosphate material includes three kinds of hydroxyapatite inverting biological ceramics, synthesizing hydroxylapatite cement one kind, β-phosphoric acid Two kinds of tricalcium Artificial Ceramic；2, composite material includes that tetracalcium phosphate/calcium monohydrogen phosphate, 62.5% type alpha tricalcium phosphate/26.8% are anhydrous Calcium monohydrogen phosphate/8.9% calcium carbonate/1.8% hydroxyapatite, 60% hydroxyapatite/40%b- tricalcium phosphate, 73%b- phosphoric acid Tricalcium/21% calcium dihydrogen phosphate/5% magnesium monohydrogen phosphate, tetracalcium phosphate/calcium monohydrogen phosphate/amorphous calcium phosphate, type alpha tricalcium phosphate/carbon 6 kinds of the synthesis cement of the formulas such as sour calcium/calcium dihydrogen phosphate is formulated as 80% tricalcium phosphate/20% calcium monohydrogen phosphate Artificial Ceramic It is a kind of；3, the mud cream of single-phase calcium sulfate preparation or totally four kinds of particle；4, siliceous bio-vitric is a kind of.Apatite, calcium sulfate are mesh Preceding clinically most commonly seen bone transplantation substitute material or constituent.Clinic lacks ideal bone transplantation substitute material at present, Mesh-structured ideal three-dimensional intercommunication, great porosity and specific surface area, degradability, osteoconductive, bone is mainly manifested in lure The characteristics such as the property led and mechanical strength cannot mostly have both at the same time.
The artificial bone with ideal three-dimensional intercommunication mesh micro-structure that clinic has been applied is animal material conversion : two of them pass through the Porous Hydroxyapatite Ceramic bone of high temperature sintering process preparation from bovine cancellous bone, and feature is It remains the three-dimensional intercommunication mesh micro-structure of bovine cancellous bone natural bone mine and ingredient is close to people's bone bone mine ingredient, there is good life Object compatibility, good osteoconductive and preferable incompressible intensity, it is anti-to exempt from but bone- xenograft immunological rejection because of high temperature sintering program It answers and pathogen importing is possible and easy to process.Porous hydroxyapatite from ox bone has the good hole of 60-90% Rate and ox bone is resourceful, aperture are 390-1360 μm, bone transplantation substitute material and bone tissue work slightly larger than 150-400 μm The ideal aperture of engineering support；The good incompressible intensity for having 1-20MPa；The Bone Defect Repari cell implanted in the body that is conducive to is raised Collection, the entrance of blood vessel, the exchange of oxygen and tissue fluid provide good physiological activity space for Bone Defect Repari cell and stick branch It holds；Its is huge the disadvantage is that the obtained bone mine-hydroxyapatite of high temperature sintering bovine cancellous bone is too stable, and degradation in vivo is too Slow length is crossed, solubility is minimum in calcium phosphorus kind bone-grafting material, and degradation speed far can not also cannot with new bone formation speeds match The skeletonization such as sustained release higher concentration calcium lack good osteogenic activity beneficial to ion, therefore, are unfavorable for the reparation and transformation of bone.
Ideal degradation speed is another important requirement of artificial bone or bone tissue engineering scaffold, ideal artificial bone degradation Speed should match with new bone formation speed, and new bone substitution is gradually degraded to while guiding new bone formation and is further provided for Space, the skeletonization such as calcium ion constantly discharged in degradation process are that the redeposited of bone mine, transformation are mentioned with metabolism beneficial to ion Ingredient is recombinated for mineral, this process may stimulate new bone formation to have potential osteoinductive to a certain degree；Artificial bone or Engineering material of bone tissue degradation speed is too fast to be unfavorable for providing Bone Defect Repari process the support and guidance of enough space-time, and is degraded Formation slow then that new bone can be hindered, substitution and moulding.The degradation of inorganic matter bone-grafting material in vivo mainly passes through two approach: body The molten drop and cell-mediated degradation process that liquid mediates.Molten drop process is material and binder hydrolysis under the action of body fluid, material Material is gradually dissociated into the molten drop process of physics of particle, molecule, ion.And cell-mediated degradation process be mainly macrophage and Biodegradation process of the osteoclast to the phagocytosis of material.The degradation process of inorganic matter bone-grafting material in vitro is formed with it Ingredient is related, and granular size, porosity, specific surface area, crystallinity and the solubility of degradation speed and material also have close phase It closes, wherein solubility is most important influence factor.Clinically calcium sulfate has in most commonly seen bone transplantation substitute material Most fast degradation speed [the degradable time is 45-72d to calcium sulfate in vivo, faster than autologous bone more than twice], in calcium phosphate material Hydroxyapatite there is most slow degradation speed [non-porous bulk hydroxyapatite in vivo 10 years all cannot be degradable], have Much larger than new bone formation speed, other calcium phosphorus compositions such as tricalcium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, polyphosphoric acids hydrogen calcium, coke The degradation rate of calcium phosphate etc. is between the two, has the degradation speed of rather moderate.In order to overcome calcining bovine cancellous bone porous The distinct disadvantage of hydroxyapatite has scientific worker to attempt that bovine cancellous bone porous hydroxyapatite turn will be calcined in the past 20 years Turn to the complex phase Apatite Ceramic of tricalcium phosphate or phosphoric acid tricalcium.It is commonly called as simple substance calcium sulfate mud cream, the cement of Paris cement Grain is the material most remote applied to bone defect filling, because of 1, good resistance to biology；2 good space filling characteristics；3 compared with Fast infiltration rate and bio-absorbable is complete；4, potential osteogenic activity；5 good bone conduction effects and because faster absorption It can be for Bone Defect Repari provides space and adopts so far.Calcium sulfate dissolves 0.2 gram or so in 100 milliliters of water under room temperature, calcium sulfate body It is being partially formed high calcium environment when interior degradation, is providing calcium source for the formation of freshman bone tissue's bone mine, is being tied with the phosphate radical etc. in body fluid It closes to promote the mineralising of new bone, local high calcium, meta-acid microenvironment in potential bone-inducting active and calcium sulfate course of dissolution It is related；Calcium sulfate degradation in vivo is also different degrees of while the high calcium environment being partially formed provides calcium source for new bone formation Osteoblast is promoted to be formed, differentiation；Calcium sulfate degradation in vivo, which forms local meta-acid microenvironment, may promote people's bone bone mine slightly soluble Drop, causes osteogenic activity albumen to appear, and is conducive to new bone formation；But the calcium sulfate mud cream or particle that clinic is applied at present are same There is the common drawback of synthetic material to be difficult to have ideal three-dimensional intercommunication mesh-structured, while the degradable time in calcium sulfate body It is faster than autologous bone more than twice for 45-72d, it is difficult to the formation of new bone is done continue, stable osteoacusis is supported, cannot be bone group The regeneration knitted provides structure basis repair cell, blood vessel that three-dimensional porous micro-structure lacks good osteoconductive and enters transplanting In object, the biology for being unfavorable for standing new bone is formed；Even if being successfully prepared into the three-dimensional intercommunication mesh knot of high porosity, high-specific surface area The calcium sulfate simple substance bracket of structure, degradation speed can faster, and intensity is worse；Local microenvironment can also be made after the molten drop of calcium sulfate material Meta-acid and be possible to cause inflammatory reaction.The advantages of synthetic composite material be can by select different degradation characteristics ingredient and its Ingredient composition makes the physical property such as degradation rate, the pH value of composite material reach certain balance, and may adsorb more kinds of people Activity in vivo albumen (signal protein), improves the bioactivity of material, more meets the desirable of bone transplantation substitute material.
In addition, the bioactivity of calcium phosphate and other biological sill may be enhanced because of incorporation bioactive ions.? It is having studies have shown that these bioactive ions can effective stimulates the protein activity, promote cell growth and bone uptake.Low dosage Strontium have promoting bone growing, inhibit the double action of bone resorption.Part calcium in low dosage strontium displacement apatite and obtain containing strontium Hydroxyapatite, not only with compared with the better histocompatbility of pure ha, osteoconductive, even have to a certain degree On osteoinductive.Human body about contains 25g magnesium, and magnesium is in human body bon e formation and all growth courses, maintenance osteocyte structure and function Energy, bone metabolism and remodeling aspect play a significant role.The magnesium phosphate calcium base bone cement of low magnesium content can significantly improve cell Adhesive capacity.It mixes magnesium calcium phosphate bone cement and is paid more and more attention because can promote implantation material and generate to become with bone tissue boundary face Novel bone reparing biological material: mix magnesium bone cement and be easier to prepare, the western countries such as New Zealand have 73%b- tricalcium phosphate/ 21% calcium dihydrogen phosphate/5% magnesium monohydrogen phosphate formula bone cement is clinically applied.Bone cement of the compound prescription containing magnesium has drop Xie Xing, the bon e formations beneficial element such as releasable calcium, phosphorus, magnesium, can be carried out degradation, ion exchange in body, does not also have after transplanting Standby three-dimensional intercommunication is mesh-structured and repair cell and blood vessel early stage is hindered to go deep into intra-graft, lacks good osteoconductive The three-dimensional mesh-structured basis of intercommunication.
We attempt sulphur, phosphorus, strontium, magnesium incorporation calcining ox bone porous support now, and the hydroxyapatite of simple substance is porous Bracket is changed into the compound porous biological support of the sulphur apatite containing magnesium and strontium containing good degradation characteristic.
Summary of the invention
It is an object of the invention to solve existing bone transplantation substitute material to be difficult to have both that good three-dimensional intercommunication is mesh-structured, machine The incorporation simultaneously of sulphur, phosphorus, magnesium, strontium is had exquisite three of natural bone mine complexity by the problems such as tool intensity, degradability and bioactivity It ties up in the mesh-structured ox calcining Grafting Cancellous Bone Bolt mine porous support of intercommunication, by calcining Niu Songzhi simple substance porous hydroxyapatite conversion The porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium of bone active ion magnesium and strontium is adulterated, of the invention is degradable The porous compound bio bracket of sulphur apatite containing magnesium and strontium have both good three-dimensional intercommunication it is mesh-structured with osteoconductive, it is degradable Property, preferable mechanical strength and biocompatibility；There is the whisker growth compared with big L/D ratio in mesh simultaneously, the ratio table of material can be increased Area may improve cell adherence.Because can produce local high calcium environment when being effectively mixed with osteogenic activity ion magnesium, strontium and degradation Calcium sulfate, compound bio bracket may have potential osteoinductive.The compound bio bracket may more meet bone The ideal condition of transplantation substitute material or bone tissue engineering stent material.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium, material group become following composite parts One of: strontium sulfate/magnesium phosphate calcium/calcium pyrophosphate, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, strontium sulfate/poly Magnesium monohydrogen phosphate calcium/calcium pyrophosphate/hydroxyapatite, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, strontium sulfate/magnesium phosphate Calcium/hydroxyapatite, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium/hydroxyl phosphorus Lime stone, strontium sulfate/calcium sulfate/polyphosphoric acids hydrogen magnesium calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium, strontium sulfate/sulphur Sour calcium/magnesium phosphate calcium/calcium pyrophosphate.
The x-ray powder diffraction analysis compound bio timbering material is porous compound for the sulphur apatite of magnesium containing active ion and strontium Biologic bracket material such as strontium sulfate/magnesium phosphate calcium/calcium pyrophosphate, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, strontium sulfate/ Polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate/hydroxyapatite, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, strontium sulfate/phosphoric acid Magnesium calcium/hydroxyapatite, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium/hydroxyl Apatite, strontium sulfate/calcium sulfate/polyphosphoric acids hydrogen magnesium calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium, strontium sulfate/ Calcium sulfate/magnesium phosphate calcium/calcium pyrophosphate etc..The constituent of compound bio bracket has preferable degradation speed more, the compound bio Timbering material may have preferable degradation.Compound bio timbering material has calcium, magnesium, strontium ion persistently to release under simulated body fluid environment It puts.The compound bio timbering material remains the exquisite three-dimensional intercommunication mesh micro-structure of ox natural bone bone mine and its good machinery Intensity can increase the specific surface area of material and at the same time there is the whisker growth compared with big L/D ratio in mesh in growth, can improve thin Born of the same parents and albumen stick.Animal Bone cancellous bone defect area transplanting observe Bone Defect Repari cell it is good in bracket stick, be proliferated, Differentiation, secretion bone matrix, the visible extremely early vascularization in bracket, intramembranous ossification of the osteogenetic process similar to physiological status；It sees The phase of examining has no obvious immunological rejection and inflammatory reaction, and compound bio timbering material is prompted to have good biocompatibility, The transplanting of Animal Bone defective region has fast and good Bone Defect Repari also to prompt the possible potential osteogenic activity of compound bio timbering material.
Preferably, ingredient containing strontium is accounted for and can be dropped in the porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium The 1-18% of the porous compound bio bracket gross mass of sulphur apatite of the solution containing magnesium and strontium is accounted for degradable containing magnesium and strontium containing magnesium component The 5-60% of the porous compound bio bracket gross mass of sulphur apatite.
Preferably, the porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium is the preparation method comprises the following steps: pass through By ox calcining Grafting Cancellous Bone Bolt mine porous support through the quaternary system processing containing magnesium source, barium source, sulphur source and phosphorus source, drying is taken out Afterwards, high-temperature calcination and obtain.
Preferably, the quaternary that ox calcining Grafting Cancellous Bone Bolt mine porous support is contained to magnesium source, barium source, sulphur source and phosphorus source One of the selection following scheme of system processing:
Scheme one: after ox calcining Grafting Cancellous Bone Bolt mine porous support is first impregnated and is evaporated in magnesium source-barium source composite solution, Enter back into hydro-thermal reaction in sulphur source-phosphorus source composite solution；
Scheme two: after ox calcining Grafting Cancellous Bone Bolt mine porous support is first impregnated and is evaporated in barium source solution, magnesium is entered back into Hydro-thermal reaction in source-sulphur source-phosphorus source composite solution.
Preferably, the hydro-thermal reaction uses incubation water heating mode, 60-90 DEG C of temperature is controlled, time 36-72 hour.
Preferably, ox calcines Grafting Cancellous Bone Bolt mine porous support and magnesium source-barium source composite solution solid-liquid ratio in scheme one For 10g:40-80mL, ox calcines Grafting Cancellous Bone Bolt mine porous support and sulphur source-phosphorus source composite solution solid-liquid ratio is 10g:40- 100mL；In scheme two, it is 10g:20-80mL, ox calcining that ox, which calcines Grafting Cancellous Bone Bolt mine porous support and the solid-liquid ratio of barium source solution, The solid-liquid ratio of Grafting Cancellous Bone Bolt mine porous support and magnesium source-sulphur source-phosphorus source composite solution is 10g:100-200mL.
Preferably, the parameter of the high-temperature calcination be 750-900 DEG C calcining 3-9 hours.
Preferably, the magnesium source is one or both of magnesium nitrate, magnesium sulfate, magnesium monohydrogen phosphate；The barium source is nitre Sour strontium；The sulphur source is the combination of sulfuric acid or sulfuric acid and soluble sulphate, and the soluble sulphate is magnesium sulfate and/or sulphur Sour sodium；Phosphorus source is the combination of phosphoric acid or phosphoric acid and soluble phosphate, and soluble phosphate is selected from magnesium monohydrogen phosphate, phosphoric acid hydrogen One of diammonium, ammonium dihydrogen phosphate, magnesium monohydrogen phosphate and diammonium hydrogen phosphate, magnesium monohydrogen phosphate and ammonium dihydrogen phosphate.
Preferably, in the quaternary system containing magnesium source, barium source, sulphur source and phosphorus source magnesium ion it is final concentration of 0.05-0.2mol/L, the final concentration of 0.05-0.5mol/L of strontium ion, the final concentration of 0.06-0.1mol/L of sulfuric acid, by sulfuric acid The final concentration of 0.05-0.5mol/L of sulfate radical, the final concentration of 1.7-15.3wt% of phosphoric acid that salt provides, the phosphorus provided by phosphate Final concentration of 0.05-0.5mol/L.Sulfate includes the sulfate in magnesium source, sulphur source.Phosphate includes the phosphorus in magnesium source, sulphur source Hydrochlorate.
Preferably, described porous its material of compound bio bracket of the degradable sulphur apatite containing magnesium and strontium can gradient drop Solution；The porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium maintains ox calcining Grafting Cancellous Bone Bolt mine porous support Three-dimensional intercommunication is mesh-structured and mechanical strength, while having the whisker growth compared with big L/D ratio in mesh, whisker draw ratio is 5- 20:1 can effectively increase the specific surface area of material, the porous compound bio bracket holes of the degradable sulphur apatite containing magnesium and strontium Gap rate 70-85%, 400-1400 μm of aperture.
Preferably, ox calcining Grafting Cancellous Bone Bolt mine porous support the preparation method comprises the following steps:
(1) bovine cancellous bone is cut into the bone item of thick 0.5-2cm or bone block obtains material bone；
(2) material bone is placed in distilled water the boiling 40-60min in pressure cooker, is then cleaned with 40-60 DEG C of drinking water dry Only, it repeats this step 4-6 times；
(3) by step (2) treated material bone in constant temperature oven 80-120 DEG C it is 12-24 hours dry, be subsequently placed in In calcining furnace, 900-1200 DEG C calcining 8-12 hours, it is cooling after ox calcines Grafting Cancellous Bone Bolt mine porous support.
The beneficial effects of the present invention are:
The present invention can stablize effectively by strontium, magnesium, sulphur, phosphorus incorporation calcining bovine cancellous bone mine porous support, by simple substance hydroxyl Apatite porous support converts the change of component degradable sulphur apatite porous compound support frame material such as sulphur containing magnesium and strontium abundant Sour strontium/magnesium phosphate calcium/calcium pyrophosphate, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/ Calcium pyrophosphate/hydroxyapatite, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, strontium sulfate/magnesium phosphate calcium/hydroxy-apatite Stone, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium/hydroxyapatite, strontium sulfate/ Calcium sulfate/polyphosphoric acids hydrogen magnesium calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium, strontium sulfate/calcium sulfate/magnesium phosphate Calcium/calcium pyrophosphate etc..The present invention is effectively mixed with osteogenic activity ion magnesium ion, strontium ion and sulfate ion, phosphonium ion etc.； Ingredient containing strontium is strontium sulfate, and strontium sulfate quality accounts for the 1.0-18% of material gross mass；It is with good degradation characteristic containing magnesium component Tricresyl phosphate magnesium calcium or polyphosphoric acids hydrogen magnesium calcium etc., the 5-60% of material gross mass is accounted for containing magnesium component；Part compound rest is containing tool There are very fast degradation speed, energy complete biodegradable and the calcium sulfate for having potential bone-inducting active ion；Part compound rest also contains There are hydroxyapatite and/or calcium pyrophosphate.
Compound bio timbering material maintains natural bone bone mine three-dimensional intercommunication mesh micro-structure and its preferable mechanical strength, There is whisker growth of the pencil compared with big L/D ratio in mesh simultaneously, whisker draw ratio is 5-20:1, can effectively increase the ratio table of material Area and improve cell adherence.Since the component of compound bio bracket has preferable degradation characteristic, compound bio branch more Frame material may have preferable molten drop characteristic.Material can still keep good mechanical strength and mesh after the molten drop of larger proportion Structure, these can be confirmed in the molten drop experiment of simulated body fluid, the visible molten drop containing magnesium, strontium sulphur apatite compound rest under Electronic Speculum With it is redeposited.Porous compound bio timbering material of the invention is when animal Grafting Cancellous Bone Bolt defective region is transplanted, it is seen that repairs thin Born of the same parents are good to be raised, sticks, Proliferation, Differentiation, secretion matrix and quick rete vasculosum are formed, and material can realize similar physiological status Intramembranous ossification, prompt the good osteoconductive of compound bio bracket and potential bone-inducting active；It is not found during observation Immunological rejection and apparent inflammation prompt compound bio bracket to have good biocompatibility.
In short, compound bio timbering material of the invention have both good three-dimensional intercommunication it is mesh-structured with osteoconductive, can drop Xie Xing, preferable mechanical strength and biocompatibility；There is the whisker growth compared with big L/D ratio in mesh simultaneously, the ratio of material can be increased Surface area improves cell adherence.Because being effectively mixed with osteogenic activity ion magnesium and strontium, some materials are also effectively mixed with can be complete Biology drop degrades and can produce the calcium sulfate of local high calcium environment, and compound bio timbering material may have potential self-bone grafting Property.The compound bio bracket may more meet the ideal item of bone transplantation substitute material or bone tissue engineering stent material Part.
Detailed description of the invention
Fig. 1 is a kind of scanning electron microscope (SEM) photograph of product of the present invention.
Fig. 2 is product of the present invention in molten drop experiment early stage calcium value (n=3, human serum calcium ion reference value 2- of simulated body fluid 2.67mmol/l)。
The scanning electron microscope (SEM) photograph of material after a kind of molten drop experiment of simulated body fluid of Fig. 3 product of the present invention.
Fig. 4 is a kind of transplantation experiments early stage histology diagram of product of the present invention.
Fig. 5 is another transplantation experiments early stage histology diagram of product of the present invention.
Fig. 6 is a kind of phase in transplantation experiments later period histology diagram of product of the present invention.
Specific embodiment
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.
In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art. Method in following embodiments is unless otherwise instructed the conventional method of this field.
The preparation example 1 of ox calcining Grafting Cancellous Bone Bolt mine porous support:
(1) the bone item that bovine cancellous bone (ox condyle of femur cancellous bone) is cut into thick 0.5cm is obtained into material bone；
(2) material bone is placed in distilled water boiling 40 minutes in pressure cooker, is then cleaned up with 40 DEG C of water, repeats this Step 6 time；
(3) by step (2) treated material bone 80 DEG C drying 24 hours in constant temperature oven, it is subsequently placed in calcining furnace Interior, 900 DEG C (10 DEG C/min of heating rate) are calcined 12 hours, and ox is obtained after furnace cooling and calcines Grafting Cancellous Bone Bolt mine porous support.Ox Calcine the preparation example 2 of Grafting Cancellous Bone Bolt mine porous support:
(1) bone block that bovine cancellous bone (ox condyle of femur cancellous bone) is cut into 1 ㎝ of thickness is obtained into material bone；
(2) material bone is placed in distilled water the boiling 60min in pressure cooker, is then cleaned up with 60 DEG C of water, repeats this Step 4 time；
(3) by step (2) treated material bone 120 DEG C drying 12 hours in constant temperature oven, it is subsequently placed in calcining furnace Interior, 1200 DEG C (10 DEG C/min of heating rate) are calcined 8 hours, and ox is obtained after furnace cooling and calcines Grafting Cancellous Bone Bolt mine porous support.
The preparation example 3 of ox calcining Grafting Cancellous Bone Bolt mine porous support:
(1) the bone item that bovine cancellous bone (ox condyle of femur cancellous bone) is cut into 0.8 ㎝ of thickness is obtained into material bone；
(2) material bone is placed in distilled water the boiling 50min in pressure cooker, is then cleaned up with 50 DEG C of water, repeats this Step 5 time；
(3) by step (2) treated material bone 100 DEG C drying 18 hours in constant temperature oven, it is subsequently placed in calcining furnace Interior, 1000 DEG C (10 DEG C/min of heating rate) are calcined 10 hours, and ox is obtained after furnace cooling and calcines Grafting Cancellous Bone Bolt mine porous support.
Total embodiment 1:
A: by the final concentration of 0.05- of magnesium ion in the quaternary system containing magnesium source, barium source, sulphur source and phosphorus source 0.2mol/L, the final concentration of 0.05-0.5mol/L of strontium ion；The final concentration of 0.06-0.1mol/L of sulfuric acid, is provided by sulfate The final concentration of 0.05-0.5mol/L of sulfate radical, the final concentration of 1.7-15.3wt% of phosphoric acid, by phosphate provide phosphorus final concentration Ingredient is carried out for 0.05-0.5mol/L.
B: weighing strontium nitrate, magnesium nitrate and first prepare strontium nitrate, magnesium nitrate solution, ox calcine Grafting Cancellous Bone Bolt mine porous support with Magnesium source-barium source composite solution solid-to-liquid ratio is 10g:40-80 milliliters；It is multiple that ox calcining Grafting Cancellous Bone Bolt mine porous support is immersed into strontium, magnesium It closes in solution, microwave is evaporated after dipping 15-30 minutes: microwave output power 300-500w, time 15-24 minute.
C: being 10g:40-100 milli by ox calcining Grafting Cancellous Bone Bolt mine porous support and sulphur source, the solid-to-liquid ratio of phosphorus source composite solution It rises and prepares sulphur source, phosphorus source composite solution, step B treated ox calcining Grafting Cancellous Bone Bolt mine porous support is immersed into dipping and hydro-thermal Reaction, hydro-thermal reaction take incubation water heating to react, and control 60 DEG C of reaction temperature, the reaction time is 12 hours.
D: 70-90 DEG C dry production 24-48 hours in porous support constant temperature oven are taken out.
E: step D treated ox calcining Grafting Cancellous Bone Bolt mine porous support is being placed in calcining furnace, 900 DEG C of (heating speed 2.5 DEG C/min of rate) calcining 3-9 hours, ox is obtained after furnace cooling calcines Grafting Cancellous Bone Bolt mine porous support converting material.
Total embodiment 2:
A: by the final concentration of 0.05- of magnesium ion in the quaternary system containing magnesium source, barium source, sulphur source and phosphorus source 0.2mol/L, the final concentration of 0.05-0.5mol/L of strontium ion；The final concentration of 0.06-0.1mol/L of sulfuric acid, is provided by sulfate The final concentration of 0.05-0.5mol/L of sulfate radical, the final concentration of 1.7-15.3wt% of phosphoric acid, by phosphate provide phosphorus final concentration Ingredient is carried out for 0.05-0.5mol/L.
B: it weighs strontium nitrate and first prepares strontium nitrate solution, ox calcines Grafting Cancellous Bone Bolt mine porous support and barium source solution solid-to-liquid ratio It is 10g:20-80 milliliters；Ox calcining Grafting Cancellous Bone Bolt mine porous support is immersed in barium source solution, microwave after dipping 15-30 minutes It is evaporated: microwave output power 300-500w, time 15-30 minute.
C: being that 10g:100-200mL preparation magnesium source-sulphur source-phosphorus source is multiple by the solid-liquid ratio of magnesium source-sulphur source-phosphorus source composite solution Solution is closed, the ox calcining Grafting Cancellous Bone Bolt mine porous support handled with magnesium source-sulphur source-phosphorus source composite solution immersion step B is soaked Stain and hydro-thermal reaction, hydro-thermal reaction take incubation water heating to react, and control 70-90 DEG C of reaction temperature, the reaction time is that 20-36 is small When.
D: 70-90 DEG C dry production 24-48 hours in ox calcining Grafting Cancellous Bone Bolt mine porous support to constant temperature oven are taken out.
E: step D treated ox calcining Grafting Cancellous Bone Bolt mine porous support is being placed in calcining furnace, 750-900 DEG C (rises 2.5 DEG C/min of warm rate) calcining 2-9 hours, product is obtained after furnace cooling.
Every a sample carries out gross examination of skeletal muscle and carries out X-ray powder diffraction (Xray diffraction, XRD) analysis；Selection Sample segment carries out carrying out displaing microstructure observing with scanning electron microscope；Carry out the animal of the molten drop experiment of simulated body fluid, bone defect healing Experiment etc..Gross examination of skeletal muscle observes general form, the intensity etc. of material, sample segment 5566 test compression intensity of INSTRON-. The molten drop experiment of simulated body fluid uses medical sodium chloride injection as simulated body fluid, detects the solid-liquid mass body of material and simulated body fluid Than being 1-2 grams: 100 milliliters, merging has in lid beaker product, and the molten drop experiment of simulated body fluid, molten drop are carried out under 37 DEG C of constant temperatures 30 days when experiment, calcium, phosphorus, magnesium, strontium ion in sample AU5800 automatic clinical chemistry analyzer detection simulated body fluid were taken every 3 days Measurement, in every 3 days replacement simulated body fluids 40%, the later period was changed without simulated body fluid for first 15 days of molten drop；It is surveyed with domestic electronic balance Determine the quality of sample after molten drop is tested 30 days and calculates degradation rate；Carry out it is molten drop experiment start before, at the end of material XRD analysis With scanning electron microscopic observation etc..Animal bone defect healing test 8 healthy new zealand white rabbits of selection, cause diameter in rabbit femoral condyle The bone defect of 8mm, using porous composite biological material carry out bone defect healing, postoperative 1,2,4,12 week execution experimental animal, into The histological examination of row bone defect healing.
Embodiment 1
605242
0.51 gram of magnesium nitrate, strontium nitrate 0.42 is taken to prepare 0.1mol/L magnesium nitrate, 0.1mol/L strontium nitrate 20 in beaker Milliliter is calcined 5 grams of absorption half an hour of Grafting Cancellous Bone Bolt mine porous support with the ox of porosity about 70-85%, low fire dry 6 in microwave × 2 minutes；2 milliliters of sulfuric acid, 3.5 milliliters of preparation 0.1mol/L sulfuric acid of phosphoric acid, 20 milliliters of 15.3w% phosphoric acid solution are taken, ox is forged It burns Grafting Cancellous Bone Bolt mine porous support investment wherein to react 12 hours for 60 DEG C, 90 DEG C drying 24 hours after taking-up；Heating 2.5 per minute DEG C to 900 DEG C, room temperature is down to furnace after maintaining 3 hours and obtains 605242A；2.5 DEG C to 900 DEG C of heating per minute, after maintaining 6 hours Room temperature, which is down to, with furnace obtains 605242E；2.5 DEG C to 900 DEG C of heating per minute is down to room temperature with furnace after maintaining 9 hours and is obtained 605242K；
Embodiment 2
605243
0.51 gram of magnesium nitrate, strontium nitrate 0.84 is taken to prepare 0.1mol/L magnesium nitrate, 0.2mol/L strontium nitrate 20 in beaker Milliliter is calcined 5 grams of absorption half an hour of Grafting Cancellous Bone Bolt mine porous support with the ox of porosity about 70-85%, low fire dry 6 in microwave × 2 minutes；2 milliliters of sulfuric acid, 3.5 milliliters of preparation 0.1mol/L sulfuric acid of phosphoric acid, 20 milliliters of 15w% phosphoric acid solution are taken, ox is calcined Grafting Cancellous Bone Bolt mine porous support is put into wherein, 60 DEG C of dippings, hydro-thermal reaction 12 hours, 90 DEG C drying 24 hours after taking-up；Every point Clock heats up 2.5 DEG C to 900 DEG C, is down to room temperature with furnace after maintaining 2 hours and obtains 605243A；90 DEG C of drying 24 hours weight 9- after taking-up 10.5 grams；2.5 DEG C to 900 DEG C of heating per minute is down to room temperature with furnace after maintaining 3 hours and obtains 605243A；Heating 2.5 per minute DEG C to 900 DEG C, room temperature is down to furnace after maintaining 6 hours and obtains 605243E；2.5 DEG C to 900 DEG C of heating per minute, after maintaining 9 hours Room temperature is down to furnace to obtain
Embodiment 3
605244
Take 1.53 grams of magnesium nitrate, 3.17 grams of the strontium nitrate preparation 0.2mol/L magnesium nitrates, 0.5mol/L strontium nitrate in beaker It 30 milliliters, is calcined 5 grams of absorption half an hour of Grafting Cancellous Bone Bolt mine porous support with the ox of porosity about 70-85%, low fire is dry in microwave Dry 6 × 2 minutes；Take 3 milliliters of 1mol/L sulfuric acid, 2.16 grams of anhydrous sodium sulfate, 0.6 milliliter of 85w% phosphoric acid, diammonium hydrogen phosphate 1.58 Gram prepare 0.3mol/L sodium sulphate, 0.1mol/L sulfuric acid, 1.7w% phosphoric acid, 30 milliliters of 0.4mol/L ammonium dibasic phosphate solution, use It submerges ox and calcines Grafting Cancellous Bone Bolt mine porous support, 60 DEG C of dippings, hydro-thermal reaction 12 hours, 90 DEG C drying 24 hours after taking-up； 2.5 DEG C to 900 DEG C of heating per minute is down to room temperature with furnace after maintaining 3 hours and obtains 605244A；2.5 DEG C to 900 of heating per minute DEG C, room temperature, which is down to, with furnace after maintaining 6 hours obtains 605244E；2.5 DEG C to 900 DEG C of heating per minute is dropped after maintaining 9 hours with furnace 605244K is obtained to room temperature.
Embodiment 4
605245
0.77 gram of magnesium nitrate, strontium nitrate 2.54 is taken to prepare 0.1mol/L magnesium nitrate, 0.4mol/L strontium nitrate 30 in beaker Milliliter is calcined 5 grams of absorption half an hour of Grafting Cancellous Bone Bolt mine porous support with the ox of porosity about 85%, low fire dry 6 × 2 in microwave Minute；Take 3 milliliters of 1mol/L sulfuric acid, 1.44 grams of anhydrous sodium sulfate, 0.79 gram of preparation 0.1mol/L sulfuric acid of diammonium hydrogen phosphate, 20 milliliters of 0.2mol/L sodium sulphate, 0.2mol/L ammonium dibasic phosphate solution submerge ox with it and calcine Grafting Cancellous Bone Bolt mine porous support, 60 DEG C of dippings, hydro-thermal reaction are reacted 12 hours, 90 DEG C drying 24 hours after taking-up；2.5 DEG C to 900 DEG C of heating per minute maintains 3 Room temperature, which is down to, with furnace after hour obtains 605245A；2.5 DEG C to 900 DEG C of heating per minute is down to room temperature with furnace after maintaining 9 hours and is obtained 605245K；
Embodiment 6
605246
Take 0.77 gram of magnesium nitrate, 1.27 grams of the strontium nitrate preparation 0.1mol/L magnesium nitrates, 0.2mol/L strontium nitrate in beaker It 30 milliliters, is calcined 5 grams of absorption half an hour of Grafting Cancellous Bone Bolt mine porous support with the ox of porosity about 85%, low fire dry 6 in microwave × 2 minutes；Take 3 milliliters of 1 mol/L sulfuric acid, 0.72 gram of anhydrous sodium sulfate, 0.4 gram of diammonium hydrogen phosphate 0.1 mol/L sulphur of preparation Acid, 30 milliliters of 0.1 mol/L ammonium dibasic phosphate solution, wherein by ox calcining Grafting Cancellous Bone Bolt mine porous support investment, 60 DEG C of reactions 12 hours, 90 DEG C of drying 24 hours weights gram after taking-up；2.5 DEG C to 900 DEG C of heating per minute is down to room with furnace after maintaining 2 hours It is warm to obtain 605246A；2.5 DEG C to 900 DEG C of heating per minute is down to room temperature with furnace after maintaining 3 hours and obtains 605246A；It rises per minute 2.5 DEG C to 900 DEG C of temperature is down to room temperature with furnace after maintaining 6 hours and obtains 605246E；2.5 DEG C to 900 DEG C of heating per minute maintains 9 Room temperature, which is down to, with furnace after hour obtains 605246K；
Embodiment 7
509032
By prepare 0.05mol/L strontium nitrate, 0.08mol/L sulfuric acid, 0.3mol/L sodium sulphate, 0.2mol/L magnesium monohydrogen phosphate, 100 milliliters of calculating ingredients of 1.7w% phosphoric acid composite solution: 1.06 grams of strontium nitrate, 5 milliliters of 1mol/L sulfuric acid, 4.26 grams of sodium sulphate, 3.46 grams of magnesium monohydrogen phosphate, 2 milliliters of 85w% phosphoric acid；1.06 grams of strontium nitrate plus 40 milliliters of solution containing strontium of deionized water preparation are first taken, is used The ox of porosity 70-85% is calcined 10 grams of dipping half an hour of Grafting Cancellous Bone Bolt mine porous support, and 500-700 watts of microwave output power It is evaporated within 24-30 minutes；Take 10 milliliters of 1mol/L sulfuric acid, 4.26 grams of sodium sulphate, 3.46 grams of magnesium monohydrogen phosphate, 2 milliliters of 85w% phosphoric acid plus Deionized water prepares sulphur, phosphorus, 100 milliliters of magnesium composite solution, submerges ox calcining Grafting Cancellous Bone Bolt mine porous support with it and immerses wherein, Beaker instead covers protection lower 70 DEG C of constant temperature dipping, takes out within hydro-thermal reaction 20 hours, 80 DEG C drying 24 hours；2.5 DEG C of heating per minute To 750 DEG C, room temperature is down to furnace after maintaining 6 hours and obtains 509032E；
Embodiment 8
601291
By prepare 0.1mol/L strontium nitrate, 0.05mol/L magnesium sulfate, 0.1mol/L sulfuric acid, 0.15mol/L sodium sulphate, 100 milliliters of 0.1mol/L magnesium monohydrogen phosphate, 1.7w% phosphoric acid compound system calculating ingredients；Strontium nitrate, epsom salt is first taken to prepare Magnesium source -20 milliliters of barium source composite solution；It is small that 5 grams of Grafting Cancellous Bone Bolt mine porous support dippings half are calcined with the ox of porosity about 85% When, 500 watts of microwave are evaporated for 8 × 2 minutes；Take 10 milliliters of 1mol/L sulfuric acid, 2.26 grams of sodium sulphate, 1.74 grams of magnesium monohydrogen phosphate, 85w% 2 milliliters of preparation 0.05mol/L sulfuric acid, 0.15mol/L sodium sulphate, 0.1mol/L magnesium monohydrogen phosphate, 1.7w% phosphoric acid of phosphoric acid are compound molten 100 milliliters of liquid；Wherein by ox calcining Grafting Cancellous Bone Bolt mine porous support investment, beaker is counter covers dipping, water under lower 90 DEG C of constant temperatures Be heat-treated 24 hours take out, 90 DEG C drying 24 hours；2.5 DEG C to 900 DEG C of heating per minute is down to room with furnace after maintaining 8 hours It is warm to obtain 603292E；
603292E
SrSO46.2%
CaSO445.3%
Ca2.89Mg0.11(PO4)248.5%.
Embodiment 9
601294
Prepare 0.3mol/L strontium nitrate, 0.05mol/L magnesium sulfate, 0.1mol/L sulfuric acid, 0.1mol/L magnesium monohydrogen phosphate, 100 milliliters of calculating ingredients of 1.7w% phosphoric acid composite solution: 3.18 grams of strontium nitrate, 0.65 gram of epsom salt, 5 milli of 1mol/L sulfuric acid Liter, 2.13 grams of sodium sulphate, 0.86 gram of magnesium monohydrogen phosphate, 85w% phosphatase 11 milliliter；First take 3.18 grams of strontium nitrate, epsom salt 0.65 Gram plus deionized water prepare strontium nitrate, 20 milliliters of magnesium sulfate composite solution；The ox of porosity about 85% is calcined into Grafting Cancellous Bone Bolt mine 5 grams of porous support investments wherein impregnate half an hour, and 500 watts of microwave are evaporated for 8 × 2 minutes；Take 5 milliliters of 1mol/L sulfuric acid, 85w% phosphorus 1 milliliter, 0.86 gram of magnesium monohydrogen phosphate of acid plus deionized water prepare 50 milliliters of composite solution, and it is more to submerge ox calcining Grafting Cancellous Bone Bolt mine with it Hole bracket, dipping, hydro-thermal process 24 hours, 80 DEG C drying 48 hours after taking-up under 70 DEG C of constant temperatures；2.5 DEG C of heating per minute To 900 DEG C, room temperature is down to furnace after maintaining 6 hours and obtains 603294E；
603294E
SrSO410.3%
CaSO459.8%
Ca2.89 Mg0.11(PO4)229.9%.
Embodiment 10
509052
By prepare 0.05mol/L strontium nitrate, 0.1mol/L sulfuric acid, 0.3mol/L sodium sulphate, 0.05mol/L magnesium monohydrogen phosphate, 100 milliliters of 1.7w% phosphoric acid, 0.5mol/L ammonium dihydrogen phosphate composite solution compound systems calculate ingredient: strontium nitrate 1.06,1mol/ 10 milliliters of L sulfuric acid, 4.26 grams of sodium sulphate, 0.86 gram of magnesium monohydrogen phosphate, 5.78 grams of ammonium dihydrogen phosphate, 2 milliliters of phosphoric acid；First take strontium nitrate 1.06 prepare 20 milliliters of strontium nitrate solution, and the ox of porosity about 85% is calcined 10 grams of Grafting Cancellous Bone Bolt mine porous support investments wherein Half an hour is impregnated, 500 watts of microwave are evaporated for 6 × 2 minutes；Take 10 milliliters of 1mol/L sulfuric acid, 4.26 grams of sodium sulphate, magnesium monohydrogen phosphate 0.86 Gram, 5.78 grams of ammonium dihydrogen phosphate, 2 milliliters of phosphoric acid plus deionized water prepare sulphur, phosphorus, 100 milliliters of magnesium composite solution, submerge ox with it Grafting Cancellous Bone Bolt mine porous support is calcined, beaker is counter to be covered lower 70 DEG C of constant temperature dipping, takes out after hydro-thermal reaction 20 hours, ph value about 2.5； 80 DEG C drying 48 hours；2.5 DEG C to 750 DEG C of heating per minute is down to room temperature with furnace after maintaining 6 hours and obtains 509052E；
Embodiment 11
512121
By prepare 0.05mol/L strontium nitrate, 0.1mol/L magnesium sulfate, 0.1mol/L sulfuric acid, 0.4mol/L sodium sulphate, 50 milliliters of 1.7w% phosphoric acid, 0.4mol/L diammonium hydrogen phosphate composite solution calculating ingredients: 0.5 gram of strontium nitrate, 1.3 grams of magnesium sulfate, 5 milliliters of sulfuric acid, 2.84 grams of sodium sulphate, 85w% phosphatase 11 milliliter, 2.64 grams of diammonium hydrogen phosphate；First take 1.3 grams of strontium nitrate, magnesium sulfate Add deionized water to prepare strontium nitrate, 20 milliliters of Adlerika, calcines the porous branch of Grafting Cancellous Bone Bolt mine with the ox of porosity 70-85% 5 grams of dipping half an hour of frame, 300-500 watts of microwave output power is evaporated for 30 minutes；Take 5 milliliters of 1mol/L sulfuric acid, sodium sulphate 2.84 Gram, 85w% phosphatase 11 milliliter, 2.64 grams of diammonium hydrogen phosphate, 50 milliliters of composite solution of preparation, with its submerge ox calcine Grafting Cancellous Bone Bolt mine Porous support, beaker is counter to be covered lower 90 DEG C of constant temperature dipping, takes out within hydro-thermal reaction 36 hours, 70 DEG C drying 48 hours after taking-up；Every point Clock heats up 2.5 DEG C to 750 DEG C, is down to room temperature with furnace after maintaining 6 hours and obtains 512121E；2.5 DEG C to 750 DEG C of heating per minute, dimension Room temperature, which is down to, with furnace after holding 9 hours obtains 512121K；
Testing result:
Material gross examination of skeletal muscle, strength detection, XRD constituent analysis and scanning electron microscopic observation
The intact prefabricated form for keeping bovine cancellous bone of various products, no fragmentation, avalanche or powdered etc. have preferable machine Tool intensity；The 1-4 sample of 10 × 10 × 10mm is shown in Table 1 with 5566 cancellous bone test compression intensity of INSTRON-.X-ray diffraction (XRD) detection confirms dipping and the calcining ox pine bone mine bracket of hydro-thermal reaction in strontium, magnesium, sulphur, phosphorus solution, through calcining after drying The porous compound bio timbering material of the degradable sulphur apatite such as strontium sulfate/magnesium phosphate calcium/pyrophosphoric acid for mixing magnesium, strontium can be converted into Calcium, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate/hydroxyapatite, Strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, strontium sulfate/magnesium phosphate calcium/hydroxyapatite, strontium sulfate/polyphosphoric acids hydrogen magnesium Calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium/hydroxyapatite, strontium sulfate/calcium sulfate/polyphosphoric acids hydrogen magnesium calcium/ Hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium, strontium sulfate/calcium sulfate/magnesium phosphate calcium/calcium pyrophosphate etc., containing strontium at The 1-18% for dividing strontium sulfate to account for material gross mass；It is magnesium phosphate calcium or magnesium monohydrogen phosphate calcium containing magnesium component, it is total accounts for material containing magnesium component The 5-60% of quality；Compound rest contains with very fast degradation speed, energy sulphur that is degradable and having potential bone-inducting active ion Sour calcium；Part compound rest also contains hydroxyapatite.Electron-microscope scanning finds (referring to Fig.1), and product maintains bovine cancellous bone certainly The main structure of the three-dimensional intercommunication mesh micro-structure of right bone bone mine, while having in mesh raw compared with the calcium sulfate crystal whiskers of big L/D ratio Long, whisker draw ratio is the specific surface area that 5-20:1 can increase material, may improve cell adherence.
1 compressive strength of table
2, the external molten drop experiment of material
The molten drop experiment of simulated body fluid uses medical chloride injection as simulated body fluid, detects the solid-liquid of material and simulated body fluid Mass volume ratio is 1-2 grams: 100 milliliters, and merging has in lid beaker, and it is real that the molten drop of simulated body fluid is carried out under 37 DEG C of constant temperatures It tests, molten drop experimental period 4 weeks, is measured with calcium, phosphorus, magnesium plasma in AU5800 automatic clinical chemistry analyzer detection simulated body fluid, With domestic electronic balance measure 4 weeks when material quality and calculate degradation rate；Carry out molten drop experiment start before, at the end of material XRD analysis and scanning electron microscopic observation etc..Experiment discovery material has preferable degradation rate (table 2), the early stage (half of simulated body fluid experiment In month) there is higher calcium ion concentration to maintain human serum normal reference value (2-2.67mmol/ in most sample simulated body fluid L) between 1-4 times of median (Fig. 2)；Also active ion magnesium, strontium release.At the end of the experiment of molten drop stent mesh become larger, machine Tool intensity is good (table 3).The XRD analysis of simulated body fluid experimental material finds, the ingredient and mass ratio of material change over time and Change, calcium sulfate and gradually decrease or disappear containing magnesium, zinc phosphorus apatite ingredient etc., timbering material fades to hydroxy-apatite Stone.Scanning electron microscope can find the molten drop of material and redeposited (Fig. 3) of mineralogical composition.
2 material of table impregnates 4 weeks degradation rates (n=3) in simulated body fluid
Compressive strength after the experiment of the molten drop of table 3
3, animal bone defect healing is tested
Transplanting early stage (1 week) i.e. visible cell, the blood vessel of porous composite biological material group enters the entire space of bracket, can See repairing cell proliferation, differentiation, secretion bone matrix (Fig. 4)；2, bone trabecula is formed within 4 weeks, freshman bone tissue has had with bracket The combination (Fig. 5) of beauty；There is within 12 weeks lamellar bone to form (Fig. 6).Bone Defect Repari is fast and observes do not find immunological rejection in the process well And apparent inflammation, material have good biocompatibility.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.

Claims (7)

1. a kind of porous compound bio bracket of degradable sulphur apatite containing magnesium and strontium, it is characterised in that: its material group becomes such as One of lower composite parts: strontium sulfate/magnesium phosphate calcium/calcium pyrophosphate, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, sulphur Sour strontium/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate/hydroxyapatite, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/calcium pyrophosphate, sulfuric acid Strontium/magnesium phosphate calcium/hydroxyapatite, strontium sulfate/polyphosphoric acids hydrogen magnesium calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate Calcium/hydroxyapatite, strontium sulfate/calcium sulfate/polyphosphoric acids hydrogen magnesium calcium/hydroxyapatite, strontium sulfate/calcium sulfate/magnesium phosphate calcium, Strontium sulfate/calcium sulfate/magnesium phosphate calcium/calcium pyrophosphate；
The porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium is the preparation method comprises the following steps: by calcining cancellous bone for ox Bone mine porous support is obtained through the quaternary system processing containing magnesium source, barium source, sulphur source and phosphorus source, after taking out drying, high-temperature calcination；
The final concentration of 0.05-0.2mol/L of magnesium ion, strontium in the quaternary system containing magnesium source, barium source, sulphur source and phosphorus source The final concentration of 0.05-0.5mol/L of ion, the final concentration of 0.06-0.1mol/L of sulfuric acid, the sulfate radical provided by sulfate are whole Concentration is 0.05-0.5mol/L, the final concentration of 1.7-15.3wt% of phosphoric acid, the final concentration of 0.05- of phosphorus provided by phosphate 0.5mol/L；
The choosing of the quaternary system processing that ox calcining Grafting Cancellous Bone Bolt mine porous support is contained to magnesium source, barium source, sulphur source and phosphorus source Select one of following scheme:
Scheme one: after ox calcining Grafting Cancellous Bone Bolt mine porous support is first impregnated and is evaporated in magnesium source-barium source composite solution, then into Enter hydro-thermal reaction in sulphur source-phosphorus source composite solution；
Scheme two: after ox calcining Grafting Cancellous Bone Bolt mine porous support is first impregnated and is evaporated in barium source solution, magnesium source-sulphur is entered back into Hydro-thermal reaction in source-phosphorus source composite solution.
2. the porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium of one kind according to claim 1, feature Be: ingredient containing strontium accounts for degradable containing magnesium and strontium in the porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium It is porous to account for the degradable sulphur apatite containing magnesium and strontium containing magnesium component by the 1-18% of the porous compound bio bracket gross mass of sulphur apatite The 5-60% of compound bio bracket gross mass.
3. the porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium of one kind according to claim 1, feature Be: the hydro-thermal reaction uses incubation water heating mode, controls 60-90 DEG C of temperature, time 36-72 hour.
4. the porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium of one kind according to claim 1, feature Be: in scheme one, ox calcines Grafting Cancellous Bone Bolt mine porous support and magnesium source-barium source composite solution solid-liquid ratio is 10g: 40- 80mL, ox calcines Grafting Cancellous Bone Bolt mine porous support and sulphur source-phosphorus source composite solution solid-liquid ratio is 10g: 40-100mL；
In scheme two, it is 10g: 20-80mL that ox, which calcines Grafting Cancellous Bone Bolt mine porous support and the solid-liquid ratio of barium source solution, ox calcining pine The solid-liquid ratio of matter bone bone mine porous support and magnesium source-sulphur source-phosphorus source composite solution is 10g: 100-200mL.
5. the porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium of one kind according to claim 1, feature Be: the parameter of the high-temperature calcination be 750-900 DEG C calcining 3-9 hours.
6. the porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium of one kind according to claim 1, feature It is, the magnesium source is one or both of magnesium nitrate, magnesium sulfate, magnesium monohydrogen phosphate；The barium source is strontium nitrate；The sulphur source For the combination of sulfuric acid or sulfuric acid and soluble sulphate, the soluble sulphate is magnesium sulfate and/or sodium sulphate；Phosphorus source For the combination of phosphoric acid or phosphoric acid and soluble phosphate, soluble phosphate is selected from magnesium monohydrogen phosphate, diammonium hydrogen phosphate, biphosphate One of ammonium, magnesium monohydrogen phosphate and diammonium hydrogen phosphate, magnesium monohydrogen phosphate and ammonium dihydrogen phosphate.
7. the porous compound bio bracket of the degradable sulphur apatite containing magnesium and strontium of one kind according to claim 1 or 2, special Sign is: described porous its material of compound bio bracket of the degradable sulphur apatite containing magnesium and strontium can gradient degradation；It is described to drop The porous compound bio bracket of sulphur apatite of the solution containing magnesium and strontium maintains the three-dimensional intercommunication of ox calcining Grafting Cancellous Bone Bolt mine porous support Mesh-structured and mechanical strength, while having the whisker growth compared with big L/D ratio in mesh, whisker draw ratio is 5-20: 1, can be effective The specific surface area of increase material, the porous compound bio brace aperture rate 70-85% of the degradable sulphur apatite containing magnesium and strontium, 400-1400 μm of aperture.
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